Hazardous Chemicals Awareness Level

7/28/2019 Hazardous Chemicals Awareness Level

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Hazardous ChemicalsAwareness Level

Wes Adams

Asheville-Buncombe TechnicalCommunity College


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HAZMAT Awareness Topics to be covered:

1. MSDS Sheets

2. NFPA System

3. UN Identification Number

4. Emergency Response Guidebook

5. Factors Affecting the Rate of Reaction6. The DOT Hazardous Materials Classes along

with the particular hazards of each class.


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MSDS Sheets An Material Safety Data Sheet (MSDS) is

a technical bulletin containing detailed

information about a hazardous substance. OSHA requires that manufacturers prepare an

MSDS for each chemical that it sells.

The MSDS contains more extensive

information than is conveyed on the label. The MSDS must accompany each chemical it

ships the first time that the chemical isshipped to that recipient.


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MSDS Sheets The following minimum information must be

provided in the MSDS:

1. The identity of the product as used on thecontainer label.

2. The chemical and common name for allingredients present in concentrations

greater than 1% and 0.1% for a cancercausing substance (carcinogen).

3. The physical and chemical properties of thehazardous components.


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MSDS Sheets4. The physical and health hazards, including

signs and symptoms of exposure and/or

prior and/or existing conditions that canwarn against exposure.

5. Primary routes of entry into the body.

6. Any known exposure limits.

7. Whether the hazardous substance is acarcinogen.

8. Precautions for safe handling and use.


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MSDS Sheets9. Procedure for spill or leak cleanup.

10. Control measures

11. Emergency first-aid procedures.

12. The date of preparation

13. The name, address, and telephone number

of the company or responsible employee

distributing the MSDS.


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NFPA System The National Fire Protection Association

(NFPA) recommends certain markings for use

on storage tanks, exterior building walls,pipelines and other relevant locations.

This procedure for identifying potentialhazards associate with a chemical is called

the NFPA 704 system.

NFPA ratings can be found on the MSDSsheet.


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NFPA System The NFPA system uses a diamond with color

coded:

1. Blue is for the health hazard.2. Red is for the flammability hazard.

3. Yellow is for the reactivity hazard.

4. White is for special hazards.

A number is placed in each section rangingfrom 0-4. A 0 means no hazard and a 4means an extreme hazard.


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NFPA System The following seven symbols are employed in the white

section of an NFPA diamond:

1. A radiation hazard symbol is a three bladed propeller.

2. The letter W with a line trough it is a caution againstapplying water.

3. The letters OXY indicate that the material is an oxidizer.

4. The letter P indicates there is a potential for the material tounder go auto-polymerization.

5. The Word ACID indicate that the material is an acid.

6. The letters ALK indicate that the material is an alkali (base).

7. The letters COR indicate that the material is corrosive.


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NFPA System4 = Severe

3 = Serious

2 = Moderate

1 = Slight

0 = None

4

1

2

P


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Identification Number UN or NA preceding a number indicates the

identity of the chemical.

UN indicates internationally transportedchemicals while NA refers to those onlytransported in the US and Canada.

In addition to these placards the UN numbermay also be inset into the appropriateplacard.


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Emergency Response

Guidebook

Also Availableon the Web
http://hazmat.dot.gov/gydebook.htm


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Emergency Response

Guidebook After obtaining the identification

number consult the North American

Emergency Response Guide Book:1. The yellow pages list the materials in

numerical order by UN ID number.

2. The blue pages list the materials inalphabetical order.


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Emergency Response

Guidebook The orange bordered pages list 172

individual guide numbers listing

emergency response actions forparticular materials.

The green bordered pages give initial

isolation and protective distances forthe highlighted entries in the yellow andblue sections.


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Factors Affecting the Rate of

Reaction There are 5 important factors which affect

rates of reactions:

Nature of the Material

Reactant Concentration

Temperature

Action of Catalysts Surface Area


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Factors Affecting the Rate ofReaction

Nature of the Material includes the chemicalcomposition of the substance and the physical state

in which it exists. For example white phosphorous ignites

spontaneously in air while wood requires an ignitionsource and water will not burn.

Generally reaction occurs fastest in the gas phase,the second fastest in the liquid phase, and muchmore slowly in the solid phase.


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Reactions in general go more quickly athigher concentrations.

For example flammable materials burn muchmore quickly at high oxygen concentrations.

Since air is 78% nitrogen and 21% oxygen by

volume, nitrogen serves to lower the oxygenconcentration and reduce the rate ofcombustion.


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As a general rule the rate of the reactionincreases as the temperature increases.

For example food spoils when notrefrigerated.

As a general rule the rate of a chemical

reaction doubles for every rise of 18oF(10oC).


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Reactions also proceed more quickly in thepresence of a catalyst.

Catalysts speed up a reaction without being usedup in the reaction.

This is usually done by lowering the activationenergy which is the energy required to initiate a

chemical reaction. The combustion of hydrogen and oxygen will not

occur without a spark unless a piece of platinum isadded and then they explode violently.


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MnO2 causes theCatalytic

Decomposition ofH

2O

2to liberate

oxygen which willincrease the

combustion rate.


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Generally reactions occur more quickly with

a greater surface area. For example a flammable liquid will burn

more quickly in a container that will allow itto assume the largest surface area.


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Burning Licompodium Powder


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Hazard ClassClass Label Class Label

1.1 Explosive 1.1 4.2 Spontaneously Combustible

1.2 Explosive 1.2 4.3 Dangerous When Wet

1.3 Explosive 1.3 5.1 Oxidizer

1.4 Explosive 1.4 5.2 Organic Peroxide

1.5 Explosive 1.5 6.1 Poison

1.6 Explosive 1.6 6.2 Infectious Substance

2.1 Flammable Gas 7 Radioactive White-I

2.2 Non-Flammable Gas 7 Radioactive Yellow-II

2.3 Poison Gas 7 Radioactive Yellow-III

3 Flammable Liquid 7 Empty

Combustible Liquid (none) 8 Corrosive

4.1 Flammable Solid 9 Class 9


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Class 1: Explosives

There are two general types of explosivematerials:

1. Chemical explosives detonate as a result of theapplication of friction, mechanical impact, or heat;usually used for demolition and other destructiveacts.

It is distinguished from gasoline and flammablegases which will seem to explode when ignited.

They are also distinguishable from nuclearexplosives, which detonate by nuclear

phenomena.


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Class 1: Explosives

Some Explosive Articles (49 CFR 173.59)

Ammunition Flash Powder Smokeless

Powder

Sounding

DevicesBlack Powder Fuse Primer Torpedoes

Bombs Fuze (Ammo) Projectiles Warheads

Charges Igniters Propellants

Fireworks Mines Rocket Motors

Flares Powder cake Signals


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Class 1: Explosives

The rapidly expanding gases often exceeds thespeed of sound and cause shock waves.

These shock waves are associated with theexplosives shattering power called its brisance.

The brisance is an important factor in choosing thecorrect explosive for a particular use, like clearing

rock for a road. Sometimes so-called chemical explosives are a

mixture of substances that appear to detonatewhich includes gunpowder and some blasting

agents.


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Class 1: Explosives

Nitrogen Triiodide is anexplosive.


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Class 2: Gases

A division 2.1 (flammable) gas is anymaterial that is a gas at 68oF or less and

14.7 psi of pressure and is one of thefollowing:

1. Ignitable at 14.7 psi when in a mixture of13% or less by volume with air.

2. Possesses a flammable range at 14.7 psi ofat least 12% regardless of the lower limit.


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Class 2

A Bunsen Burner Flame is fueled by Naturalgas. Different Metals in the flame will changethe flame from blue to different colors. This

also works for liquids.


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Class 2: Gases

A division 2.2 (non-flammable) gas isany material or mixture that does one

of the following:1. Exerts in its packaging an absolute

pressure of 41 psi or greater at 68oF.

2. Does not meet the definition ofdivision 2.1 or 2.3


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Class 2: Gases

A small amount of water is placed into acan and heated when rapidly cooled thewater vapor condenses leaving a vacuumwhich allows the air pressure to crush thecan.


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Class 2: Gases

A division 2.3 (poison by inhalation) gas is amaterial that is a gas at 68oF or less at 14.7

psi and is one of the following:1. Known to be so toxic to humans as to pose

a health hazard during transportation.

2. In absence of data on human toxicity, istoxic to laboratory animals and has and LC50(lethal concentration 50% of the time) lessthan 5000 mL/m3.


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Class 2: Gases

Some examples of toxic gases are:

Carbon Monoxide

Hydrogen cyanide

Sulfur dioxide

Hydrogen Sulfide Nitrogen Dioxide

Anhydrous Ammonia


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Class 2: Gases

Copper and Nitric Acidgenerate Nitrogen Dioxide


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Class 3: Flammable Liquids

The DOT defines a flammable liquid as either ofthe following:

1. Any liquid having a flash point not more than141oF.

2. Any liquid with a flash point at or above 100oFthat is intentionally heated and offered fortransportation or transported at or above itsflash point within bulk packaging.

A combustible liquid has a flash point above

141oF and below 200oF


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Burning Methanol


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Large amounts of compressed gases or liquefiedgases are transported in large tanks pulled behindthe vehicle or as its own separate rail car.

Such a tank exposed to direct flames will rupture.

If a liquefied gas is flammable a Boiling LiquidExpanding Vapor Explosion (BLEVE) can occur.

A BLEVE occurs when a released liquid is rapidlyheated to temperature above its boiling point.

Some BLEVEs have resulted in fireballs with radiiof 900 ft.


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Class 4: Flammable Solids

The DOT defines a flammable solid as anyof the following:

1.

Any of several wetted explosives2. Any of several self-reactive materials that

are thermally unstable and can undergo astrongly exothermic (gives off heat)

decomposition even without theparticipation of atmospheric oxygen

3. A readily combustible solid.


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Burning Magnesium in thepresence of Carbon dioxide.


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The DOT defines a spontaneouslycombustible material as either of thefollowing:

1. Apyrophoric material is a liquid or solid thateven in small quantities and withoutexternal ignition source can ignite withinfive minutes after coming in contact withair.

2. Aself-heating material is a material thatwhen in contact with air and without anenergy supply is liable to self heat.


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Phosphorus in Air


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The DOT defines a dangerous when wetmaterial as a material that, by interaction

with water, is likely to becomespontaneously flammable or to release aflammable or toxic gas or vapor at a rategreater than 28 in3/lb (1 L/kg) per hour.


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Calcium Carbide and Waterliberate flammable acetylene

gas.


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Release H2 from water Release H2 from acids No release of H2

Cesium Aluminum (steam) Bismuth

Lithium Manganese (steam) Copper

Rubidium Zinc (steam) Mercury

Potassium Chromium (steam) Silver

Barium Iron (steam) PlatinumSodium Nickel Gold

Calcium Tin

Magnesium Lead


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Class 5: Oxidizers and OrganicPeroxides

The DOT defines two classes of oxidizers:

1. An oxidizer (division 5.1) is a material

that can cause or enhance thecombustion of materials, generally byyielding oxygen.


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PotassiumChlorate and

Gummy Bear

Ammonium NitrateZinc and Water

Copper Silver

Redox


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An organic peroxide (division 5.2) is anorganic compound containing oxygen in

the bivalentOO structure. Organic peroxide formation is especially

susceptible in some ethers especially:

diglyme, diethyl ether, dioxane, glyme,isopropyl ether, tetrohydrofuran.


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Test for organic peroxides at theneck of old ether bottles beforeopening.


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Class 6: Poisonous andInfectious Materials

The DOT defines poisonous and infectious materials asfollows:

1. A poisonous material is a material other than a gas that

is known to be toxic to humans to present a hazardduring transport or:

a. Is presumed to be toxic because of data obtained fromtests performed on animals.

b.

Is an irritating material with properties similar to tear gasand causes extreme irritation, especially within confinedspaces.

Examples include cyanide containing salts, asbestos, andpesticides.


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2. An infectious material is a viable micro organismor its toxin that causes or can cause disease in

humans or animals. Potentially infectious substances include:

Blood and blood products

Saliva, vomit, urine

Semen or vaginal secretions

Skin, tissue, cell cultures

Other body fluids (particularly if blood is visible).

l d


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Class 7: Radioactive Materials

A radioactive material is any material or anycombination of materials that spontaneously

emits ionizing radiation having a specificactivity greater than 70 Becquerels per gram.

Radioactive White-I, Yellow-II, and Yellow-IIIalerts emergency response workers to

increasing radioactivity. White-I is the least radioactive and Yellow-III

is the most radioactive.


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Class 7: Radioactive Materials

A Geiger Counter is used to measure

radioactivity.


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Class 8: Corrosive Materials

A corrosive material is both of the following:

1. A liquid or solid that causes visible

destruction or irreversible alterations in skintissue at the site of contact.

2. A liquid that has a severe corrosion rate onsteel or aluminum, as measured in

accordance with certain prescribed DOTtesting procedures.


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Class 8: Corrosive Materials

Sodium Biarbonate + HClliberates CO2 gas.

Magnesium + HClliberates H2 gas

Cl 9 Mi ll


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Class 9: MiscellaneousHazardous Materials

The DOT defines a miscellaneous hazardousmaterial as a material that presents a hazardduring transportation, but is not included in any

other hazard class. These materials are any material that has

anesthetic, noxious, elevated-temperaturesubstances, hazardous wastes and marine

pollutants, and magnetized materials. ORM-D materials are also class 9.

Cl 9 Mi ll


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Class 9: MiscellaneousHazardous Materials

Hot water whentransported is an elevated

temperature material an istherefore Class 9


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Hazardous Chemicals Awareness Level